CN1503922A - Electrooptical display with multilayer structure achieved by varying rates of polymerization and/or phase separation - Google Patents
Electrooptical display with multilayer structure achieved by varying rates of polymerization and/or phase separation Download PDFInfo
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- CN1503922A CN1503922A CNA028070291A CN02807029A CN1503922A CN 1503922 A CN1503922 A CN 1503922A CN A028070291 A CNA028070291 A CN A028070291A CN 02807029 A CN02807029 A CN 02807029A CN 1503922 A CN1503922 A CN 1503922A
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
- G02F1/13394—Gaskets; Spacers; Sealing of cells spacers regularly patterned on the cell subtrate, e.g. walls, pillars
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
- G02F1/139—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on orientation effects in which the liquid crystal remains transparent
- G02F1/141—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on orientation effects in which the liquid crystal remains transparent using ferroelectric liquid crystals
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- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Mathematical Physics (AREA)
- Dispersion Chemistry (AREA)
- Liquid Crystal (AREA)
- Polymerisation Methods In General (AREA)
Abstract
A method of manufacturing a liquid crystal display device is disclosed. The method comprises filling the space between two facing substrates with a mixture of pre-polymer and liquid crystal material, applying an external source of energy to initiate a polymerization, wherein as the polymerization proceeds a phase separation of the polymer and liquid crystal is generally also proceeding, after initiation of polymerisation and before completion thereof, adjusting a parameter that affects one or both of the rates of polymerization and phase separation, so as to produce a variation in the polymerized structure, wherein the variation is a result of the rates of polymerization and phase separation being adjusted during the course of polymerization.
Description
Background of invention
The invention relates to liquid crystal and the demonstration of other electronics.
The commercial high request that shows for electronics is to approach as much as possible with light, and simultaneously to comprising the impulsive force that causes because of bump, extruding, bending, leave etc., still maintain soundness and protective capacities highly.In field of portable electronic apparatus, such as cell phone and personal digital assistant (PDAs), its size and weight are vital factors to the business success of product, and the damage of the demonstration in these devices is a main cause of the maintenance at present and the return of goods.In addition, in fact known the concentrating in some fields of demand to the electronics demonstration: so-called " Electronic Paper ", wherein, can roll or fold as traditional paper if electronics shows, as a kind of product, will more force to show to replace fibre paper.If demonstration is suitable for user's health then can wear electronic equipment, as counter or multi-function watch, will be more happy for user.Have the core card of strict flexible durability test performance standard, flexible demonstration can be housed, and still meet those standards.For many years, in showing the boundary, replacing glass matrix with plastic sheeting in the demonstration has become an active research field.
For the application in flexiplast shows, developing several different technology.Electrophoresis showed is a kind ofly to obtain image by the rapid migration of electrophoresis-particulate in soliquid.In the soliquid of dyeing, light diffusing particles moves by static electric power.Particle moves towards the observer, and in this case, what the observer saw mainly is white particles, perhaps, moves towards outlying observation person's surface, and in this case, white particles is sheltered by dark-coloured dyestuff.
It is the another kind of display technique of attempting on plastic matrix that cholesterol shows.When being clipped between the conductive electrode, cholesteric liquid crystal materials can be clipped in two kinds of stable states-so-called focus circular cone attitude and plane attitude-between conversion, wherein the helical structure of liquid crystal has different orientations.Under focus circular cone attitude, helical structure does not form straight line, and liquid crystal is transparent.Under the attitude of plane, the axle of helical structure causes mainly producing monochromatic the propagation by showing all perpendicular to the surface that shows.
Gyricon by Xerox development shows it is to be made by micro-pearl, and the flexible elastomeric matrices random dispersion by oil-filled cave also is fixed on two places between plastic sheet.Bead has contrasty hemisphere, be black on the side, and opposite side is a white.White one side is strong reflection, and black one side is absorbing light then.When applying electric field, each hemisphere has unique intrinsic charge, causes generation power on bead, and the axle of ball does not form straight line with electric field.Be used to show that ball one side that is presented depends on the polarity to electrode application voltage.Under these three kinds of situations, they have some positive features at all, such as, high-contrast and with the compatibility of plastic matrix, they generally need high driving voltage, have slow response time, and incompatible with the drive electronics of commercial acquisition.
Because liquid crystal display (LCDs) needs very low driving voltage when it is changed, their quickish response times, so very wide drive electronics application and important intelligence and manufacturing investment are very attractive.Done many trials for developing LCDs, compatible in order to make them with plastic matrix, mixed liquid crystal in polymer substrate, the demonstration (PDLCDs) that example is a polymer dispersed.PDLCD by before assembling shows with liquid crystal with give polymers and be blended in the solution mutually and make.Assembling utilizes ultraviolet light to make polymer cure after showing usually.Between polymerization period, LC can separate and form trickle droplet from polymkeric substance.Because the LC droplet does not contact with any alignment layers, so the orientation of molecule is at random, and by the droplet disperse light.Electrode application voltage to PDLCD can make the LC molecule form arrangement, becomes transparent in causing showing.Show as other pliabilities, the exigent driving voltage of PDLCD, generally not compatible with existing drive electronics.Prior art, such as U.S. patent Nos.4688900,5321533,5327271,5333094,5434685,5473450,5504600,5530566,5583672 and 5949508, utilizing light to make polymer poly fashionable, all utilized being separated of LC/ polymeric blends as curing mechanism (photopolymerization).
Now developed a lot of methods, with the LC/ polymer architecture that obtains anisotropically to disperse, their driving voltage all is lower than and obtains in PDLCD.U.S. patent No.5949508 has described a kind of method, this method is that LC is configured on the relative matrix with polymkeric substance, obtained layer structure, this has just reduced the needed driving voltage of conversion equipment, but produce a kind of structure, wherein, the locating surface that in fact only on a matrix, has friction.And demonstration row or electrically conerolled birefringence (ECB) of this structure subtend is effectively, but it is difficult to the formation demonstration, and such as the liquid crystal display of twisted-nematic phase (TN) and supertwist nematic phase (STN), these show that requiring usually is locating surface on two matrix.U.S. patent Nos.5473450 and 5333074 has described the method for utilizing mask only partial devices to be exposed to light source and locate polymkeric substance when photopolymerization.(～0.3mm) the polymer architecture of level size, still, processing is difficulty quite, because photomask must be consistent with the electrode structure in the device, and must use expensive parallel UV light source can to obtain to be about pixel.Because the intrinsic dispersion of LC/ polymeric blends is so be difficult to obtain to be far smaller than the structure of 0.3mm.U.S. patent No.5473450 points out to form the pattern of light trigger on alignment layers, but the exigent degree of accuracy of this method, the light trigger of screening sedimentation chemistry on matrix.ITO electrode for cleaning is difficult to obtain the accurately silk screen mask of arrangement, and directly introduces chemicals on the polyimide locating surface, can cause LC not arrange locating surface well, very poor demonstration outward appearance and lower manufacturing yield occur.
Except the damage problem because of the bump and the generation of falling, glass matrix shows the limit that also is difficult to stand temperature.When temperature displayed circulation time between cold and hot, between partition and liquid crystal fluid, produce little space sometimes.When space small-sized, to notice enough that usually demonstration will be returned repairing.The space is owing to LC and generally is to exist the mismatch of thermal expansivity to cause between glass or the plastics partition.When at room temperature assembling glass matrix demonstration and sealing, its volume is just at this moment fixing basically.When showing cooling, LC and separator material will shrink, because the mismatch of thermal expansivity and in the intermittence of the machinery at partition place, stress is positioned at around the partition, and the generation space.Originally, the space is the small size vacuum, or pressure is very low, and still, more the LC volatile component of volume is shifted in the gas phase soon, and is full of the space, and forms low-yield equilibrium state.When demonstration turns back to room temperature, the steam of filling the space will stop the space to enter LC from absorption, this danger that just lies dormant usually.Show that the fabricator has solved this class problem, in additive method, by using the partition of special manufacturing, this partition has more soft, preferably external coating around glass core or plastic core.The effect of outer suitable layer is to alleviate the stress that is run into when showing thermal cycle, therefore can prevent the space.Because the preparation difficulty of these partitions, they are usually than the expensive 10-20 of common partition times, so only just use when absolute demand.
Invention is concise and to the point
Usually, feature of the present invention is a kind of method of making liquid crystal indicator, this method comprises with the space between two matrix of facing of potpourri filling of giving polymers and liquid crystal material, and use extra power initiated polymerization, wherein, when polymerization is carried out, polymkeric substance and liquid crystal generally also are separated, before polymerization begins back and polymerization end, regulate influence polymerization and be separated in one of speed or the parameter of both speed, so that along perpendicular to two directions in the face of matrix, in the structure of polymerization, change, wherein, this variation is the result who adjusts the polymerization and the speed that is separated in polymerization process, so that produces at least the first and second layers in liquid crystal indicator.
In preferred embodiments, can be in conjunction with in the following feature one or more.At least form first and second layers in liquid crystal indicator, first and second layers can superpose each other, and are positioned at the different spacing of facing on the matrix direction along perpendicular to two.Wherein, first and second layers structure is different, and this is because during cambial, polymerization is different with the related rate that is separated.Variation in the paradigmatic structure can change in a continuous manner, because in the time that forms structure, polymerization is different with the speed that is separated.Polymerization rate can be regulated.Polymerization rate can change sharp, changes to cause polymerization rate to produce stepwise.So that the continuous function of generation time, this such as can adopt at form of varying function, index curve or other mathematical functions.Can regulate the intensity of light source that influences polymerization rate, can be ultraviolet light with adjusting polymerization speed, light source.The scalable speed that is separated, the speed that is separated can change sharp, changes so that produce stepwise in the speed that is separated.Can regulate being separated, so that the continuous function of generation time, this such as can adopt at form of varying function, index curve or other mathematical functions.Can regulate temperature, with the adjusting speed that is separated.Ground floor mainly is a polymkeric substance, and the second layer mainly is the potpourri of polymkeric substance and liquid crystal material.The present invention also comprises the 3rd layer, and is different with the structure of the ground floor and the second layer, because in the time that forms these layers, polymerization is different with the related rate that is separated.The 3rd layer mainly is liquid crystal material.The 3rd layer of droplet that can around polymkeric substance, contain liquid crystal material.The liquid crystal droplet can contact with matrix.Giving polymers and liquid crystal can be a kind of like this composition, and can carry out polymerization under a kind of like this condition, that is, give the Combination of polymers and liquid crystal material by change, and determine first and second layers structure.Giving polymers and liquid crystal can be a kind of like this composition, and can carry out polymerization under this condition, that is, give the viscosity of polymers and liquid crystal material and can determine first and second layers structure by change.Viscosity is the relative viscosity of giving polymers and liquid crystal.Viscosity also can be the absolute viscosity of giving polymers and liquid crystal.
Other features and advantages of the present invention can be clearer and more definite from as detailed below instructions and claim.
Brief description of the drawings
Fig. 1 is the sectional view of liquid crystal indicator, wherein, before being exposed to apparent light, uses the spherical partition that applies with light trigger.
Fig. 2 is the sectional view of liquid crystal indicator, wherein, after being exposed to apparent light, uses the spherical partition that applies with light trigger.
Fig. 3 is the sectional view of liquid crystal indicator, wherein, after polymerization and being exposed to apparent light, uses the spherical partition that applies with accelerator.
Fig. 4 is the sectional view of liquid crystal indicator, has wherein used the barrier film as net.
Fig. 5 is the sectional view of liquid crystal indicator, wherein, before being exposed to apparent light, has used the spherical partition that scribbles light trigger and the initiation of unstructuredness polymkeric substance or strengthen (PIE) composition.
Fig. 6 is the sectional view of liquid crystal indicator, wherein, after being exposed to apparent light, has used the spherical partition that scribbles light trigger and the initiation of unstructuredness polymkeric substance or strengthen (PIE) composition.
The detailed description of invention
According to the present invention, in preferred embodiments, utilize following steps assembling liquid crystal indicator:
1. matrix is to have low-level birefringent flexible polymeric material, improving the optical quality of final products, and has the glass transition temperature greater than 150 ℃, to be easy to various dryings and baking operation.The polymkeric substance that satisfies these requirements is polyethersulfone (PES).The vapor barrier layer is coated on the outside surface of matrix, and to improve reliability and the life of product that shows, the vapor barrier layer generally is made of the film laminating structure of monox and other polymkeric substance.
2. matrix normally scribbles the vacuum deposited layer of tin indium oxide (ITO), and it is a kind of transparent conductor.Then, make ITO form pattern by chemistry, electron beam or laser-induced thermal etching.
3. with about 10% the light-initiated polymers that gives, such as the liquid crystal of, Norland Products NOA-65 and 90%, such as MercK E7, the preparation potpourri.Give the improvement of polymers preparation, make whole light triggers by removing in the preparation.
4. polyimide solution is coated on the ITO side of at least one matrix, and toasted 1 hour down at 150 ℃.Then with the polyimide surface friction, to form the alignment layers of liquid crystal.
5. diameter is that the glass partition of 3-3.5 μ m is to utilize 1.25% hydrofluoric acid solution corrosion surface 10 minutes, is suspended in simultaneously in the solution in the supersonic oscillations groove.After the washing, contain initiating agent and short stick, in the solution such as silane, and make the partition of corrosion be coated with the potpourri of methacrylate silanes and light trigger, then partition is sprayed into the top of vertical dry post by partition is immersed in, and on matrix.Silane is at silane/interior surfaces of glass place, by chemical bond, and makes polymer dispersed in silane and can improve combination between glass and the polymkeric substance at silane/polymkeric substance inside surface place.
6. be deposited on a large amount of partitions that (density is at least 30 partition/mm on the stromal surface
2).Generally, partition tends to be randomly dispersed on the whole stromal surface.
7. make LC/ give the potpourri of polymers, be deposited on capacity on two inside surfaces of matrix, and hypothallus is forced together, on matrix up and down, will keep simultaneously the suitable arrangement between the ITO pattern.
Then with the exposed at both sides of unit under UV light, this splits with regard to causing the light trigger around the partition, and discharges free radical.Begin to carry out polyreaction by concentrating on each partition priming site on every side, each spacer deposits initiating agent.
9. when polymerization begins,, and polymerization rate is set,, changes LC and the rate of diffusion of giving polymers simultaneously by the conditioned reaction temperature by adjusting UV intensity.Viscosity by giving polymers and by selecting LC and give polymers obtaining the optimum degree of mixing of two kinds of liquid, and can control rate of diffusion.By regulating diffusion and reaction rate, the LC/ polymer architecture that is produced can provide desired form.Though depend on its dependent variable that influences phase separation than number, in order to be separated fully, typical temperature surpasses 45 ℃, gives polymers viscosity less than 1000cps.
The demonstration that produces be have fully flexible, by the amount of bow of stipulating in the bending test of in US patent No.6019284, describing at least, can be crooked and do not have potential danger, it is for referencial use to introduce the document.
In all cases, do not need polymkeric substance near each partition, to form, do not need polymkeric substance to expand to another matrix fully yet from a matrix.For example, some partitions can be coated with by PIE material of no use, or can not exclusively be coated with.
There is not to be extended to from a matrix fully the polymer support of another matrix, still help creating the isolated area of liquid crystal, therefore, can improve the bistability of some ferroelectric liquid crystal material, if liquid crystal layer is divided into discrete droplet along a matrix, then can present improved bistability.
In another embodiment, polymerization initiator is without photoactivation, but " accelerator lacquer " type.When using accelerator lacquer initiating agent, finish the coating of partition by the early stage method of describing of picture, still, enter with after the partition of initiating agent coating contacts in the LC/ mixture of polymers, begin polymerization sometimes automatically.To solidify the preceding time of beginning in order prolonging, can at room temperature to carry out lamination.After finishing lamination, the rising temperature is to increase LC and the diffusivity of giving polymers.In addition, be chosen in the superoxide in the aromatic amine that gives in the polymers preparation and the lacquer,, when in conjunction with rate of diffusion of giving polymers and LC and the spacing in the viewing area, cause being positioned at the polymkeric substance of partition peripheral region so that provide appropriate free radical to produce speed.
In another embodiment, give the polymers preparation and still keep its light trigger composition, but partition still is coated with toughness promoter such as silane, apply with accelerator or other light trigger.Usually the active component in the accelerator is a tertiary amine, as dimethylamino benzene.In this case, curing can cause by accelerator and light.The accelerator reaction can be carried out time enough, so that most of polymkeric substance is positioned at around the partition.Then, only start light source, make the deposition of any residual polymer be close to light source, as shown in Figure 3 along matrix in a side.This specified scheme can be further refining by the bistable liquid crystal of energy,, has the ability of 2 of maintenances or a plurality of electric light attitudes that is, and without any electric field.Some examples of this bistable state or multistable state liquid srystal are liquid crystal of ferroelectric type or anti-ferroelectric type.In another refining scheme, change reaction rate to produce a kind of structure in polymerization process, in this structure, the liquid crystal droplet that is dispersed in the polymkeric substance produces on the locating surface near light source, and liquid crystal thin layer is created on the locating surface relative with light source, as shown in Figure 4.Two surfaces are with a kind of like this pattern arrangement, so that the arrangement of formation LC molecule on two faces, but the LC of known droplet sealing with regard to keeping bistable state, is the most durable structure.
In a further preferred embodiment, be to utilize following technology assembling liquid crystal indicator.
1. matrix is to have low-level birefringent flexible polymeric material, improving the optical quality of final products, and has the glass transition temperature greater than 150 ℃, to be easy to various dryings and baking operation.The polymkeric substance that satisfies these requirements is polyethersulfone (PES), and the vapor barrier layer is coated on the outside surface of matrix, and to improve reliability and the life of product that shows, the vapor barrier layer is made of the film laminating structure of monox and other polymkeric substance usually.
2. matrix scribbles the vacuum deposited layer that is generally tin indium oxide (ITO), and it is a kind of transparent conductor.Then, make ITO form pattern by chemistry, electron beam or laser-induced thermal etching.
3. with about 10% the light-initiated polymers that gives, such as the liquid crystal of Norland Products NOA-65 and 90%, such as MercK E7, and the preparation potpourri, correctability gives the polymers preparation, so that can remove whole light triggers from preparation.
4. polyimide solution is coated on the ITO side of at least one matrix, and toasted 1 hour down at 150 ℃.Grind polyimide surface then, to form the alignment layers that liquid crystal is used.
5. utilize 1.25% hydrofluoric acid solution that diameter is the glass partition surface corrosion of 3-3.5 μ m 10 minutes, be suspended in simultaneously in the solution in the supersonic oscillations groove.After the washing, by partition being immersed in the solution that contains initiating agent and short stick such as silane, and make partition scribble the potpourri of methacrylate silanes and light trigger the partition of corrosion, the top that then partition is sprayed into vertical dry post arrives on the matrix.Silane is by the chemical bond in silane/glass interface, and at silane/polymer interface place, polymer diffusion is advanced in the silane, and can improve the combination between glass and polymkeric substance.
6. partition is deposited on the stromal surface, and density is at least 30 partition/mm
2
7. the PIE unit of about 25% partition size is added in the potpourri that LC/ gives polymers, sectional density is about the twice of partition density.
8.LC/ give the potpourri of polymers, be deposited on capacity on the inside surface of two matrix, and hypothallus is forced together, simultaneously between the ITO pattern on the matrix up and down, keep suitable arrangement.
Then with the exposed at both sides of element in UV light, around partition, produce light trigger and split, and discharge free radical.Then, to concentrate on the initiation point around each partition or to carry out polyreaction with the PIE composition that initiating agent deposits.
10. when beginning to carry out, polymerization rate is set, changes LC and the rate of diffusion of giving polymers by the conditioned reaction temperature simultaneously by regulating UV density.Viscosity by giving polymers and by LC and the suitable selection of giving polymers to obtain the suitable degree of mixing of two kinds of liquid, also can control rate of diffusion.By regulating diffusion and reaction rate, can design the LC/ polymer architecture of generation, to obtain desired form.In order fully to be separated, temperature should surpass 45 ℃, and the viscosity of giving polymers is less than 1000cps.
If unstructuredness PIE unit is greater than 50% partition size, then they will roughly 2 tie up stochastic distribution lattice network.During polymerization, polymkeric substance will grow up to approximately spherical shape from the form of PIE, and along with abundant polymerization will be extended on the matrix, the polymkeric substance that makes arrangement is attached between the matrix.,, if before assembling shows the NSPIE unit is mixed in the potpourri that LC/ gives polymers less than 50% partition size for unstructuredness PIE (NSPIE) unit, then the lattice network of NSPIE will be 3 dimensions.Under about 25% partition size, and have the lattice network spacing of about 50% partition diameter, then form perforate, the polymer spheres of overall network and with LC filling copolymerization tagma (Fig. 6).This ad hoc structure is used for bistable demonstration, the intermittence of highdensity machinery wherein is provided, and this has increased the hysteresis of the required optics of bistable state and the permanance of appending.
In another embodiment, polymerization initiator is not to utilize photoactivation, but " accelerator lacquer " type.When using accelerator lacquer initiating agent, can finish coating by the method for early stage description to partition or NSPIE unit, after the partition that makes LC/ mixture of polymers and initiating agent coating or NSPIE unit contacted, sometimes, the polymerization meeting began automatically.To solidify the preceding time of beginning in order prolonging, can at room temperature to carry out lamination.After finishing lamination, the rising temperature, to increase LC and the diffusivity of giving polymers, in addition, selection give in the polymers preparation aromatic amine and the lacquer in superoxide, to provide suitable free radical to produce speed, when in conjunction with rate of diffusion of giving polymers and LC and the spacing in the viewing area, can make polymkeric substance be positioned at the peripheral region of partition or NSPIE unit.
The NSPIE unit can be to be generally used for the glass in the display device or the ball or the rod of plastics, and in this case, for this special demonstration, the unit is less than partition.Because the NSPIE unit at most only contacts with a matrix, when extruding, the NSPIE unit does not push to matrix with excessive power.As a result, the NSPIE unit can be non-smooth form, can not work the mischief to matrix when extruding.In addition, because the NSPIE unit is not to be used for determining the matrix spacing, so they can change shape and size in wide range, and still can realize their function satisfactorily.Compare with can be used for standard partition unit, for the NSPIE unit, these factors allow it to use the more material of wide range of types.For example, a kind of newtype or new material are called the nanoaperture material, and be obtained, and its intermediate pore size, and total surface area all can specify and make.These materials mainly are pottery or monox composition, and by sintering, aerosol processing perhaps carries out chemical treatment by existing inorganics or glass and forms.Yet, almost, all these situations, the size of the particle that is obtained and often is coarse or/and shape all is difficult to control, is that sharp keen surface-they can not be used as the partition unit in display device sometimes.Yet as the NSPIE unit, their porosity can be controlled, so that the predetermined relatively volume storage ability of light trigger, accelerator or other polymerization enhancing ingredients to be provided.For example, when using the work of accelerator or light trigger, need the concentration of these compositions in demonstration for always giving the 0.1-5% of polymers.By regulating the size of NSPIE unit, quantity and porosity can obtain this concentration.
Before assembling, also the NSPIE unit directly can be deposited on the matrix.This can combine in the potpourri that LC/ gives polymers and finish being mixed into the NSPIE unit usually, and will make polymkeric substance and matrix form stronger combining.
When at the specified point initiated polymerization, can use two or more light triggers to control with different spectral responses.Because when the photon energy of light source surpassed definite threshold values, light trigger split, light trigger generally is that wavelength is had susceptibility less than the light of particular value, therefore, to the light trigger of visible light sensitivity usually also to the ultraviolet sensitivity.An embodiment utilizing this feature is that the light trigger with the visible light sensitivity applies the partition unit and with the light trigger coating NSPIE unit of UV sensitivity.At first will assemble thing and be exposed to visible light, only the polymkeric substance around the partition will be cured.And then will assemble thing and be exposed to UV light, make to be present in still that any other polymers that gives is cured in the solution that LC is arranged.
In another embodiment, other polymerizations strengthen compounds, as short stick, or adjuvant,, can join among NSPIE unit whole such as the carbamate that can before fracture characteristics, improve extensibility, or in some subsystem.The NSPIE unit that is deposited on the matrix can have fracture preceding improvement extensibility but the adjuvant (making that therefore it is more responsive to extruding) of reduction material hardness, and the NSPIE unit that is mixed in the LC/ mixture of polymers can not have this adjuvant, so it has higher hardness.By this way, can further improve peel strength.
A kind of acceptable polymkeric substance is an acryloid cement, the extensive selectivity that it has the good optical transparency and makes the optical grade types of material.Other polymkeric substance also can use, and for example, epoxy or urethane polymer be not though the polymkeric substance of these types has the optical characteristics that is equal to those acrylic acid.Acryloid cement is a kind of bonding agent of reactive cross-linked structure, and it solidifies by means of free radical causes.They are based on the methyl-prop allyl ester monomer, and are cured by other polymerization.The formation of free radical has caused the curing of chain reaction suddenly and rapidly of bonding agent.On the other hand, be the polycondensation of representative with carbamate and epoxy, be near constant rate of speed, normally carry out being lower than under the reaction velocity.Be used to cause the generation of the free radical of acrylic substrate bonding agent polymerization, can realize by redox reaction, such as comprising xylidin and superoxide.Because the character of chain reaction is exactly that free radical can expand to monomer from monomer, the curing of itself can cause point from polymerization and expand to 2.5mm.The result of this curing expansion does not fully mix to obtain sufficient curing accelerator and monomer.This just causes some other curing, and wherein accelerator can be present on the face that can be used for part primary coat and storage with the form of lacquer or film.In another relevant curing, the saying in the industry is called " honeymoon " or " nothing-mixing ", uses two parts of bindings, and when they were contacted with each other, (without any need for mixing) can produce enough free radicals, with abundant polymerization all material.
Acrylic acid in some instances, also can be implemented by visible light by being exposed to wavelength less than also being cured in the ultraviolet of 400nm.Under the situation of Photocurable adhesive, the free radical source is called light trigger, and causes being exposed to light time formation free radical.As the compound at the light trigger of the light of 200～300nm scope is benzoin ethers, active Benzophenones and relevant compound, and benzyl dialkyl amido morpholinyl ketone is an example of the light trigger of visible wavelength activity.In known method of splitting, make light trigger resolve into the fragment of free radical by light as light.In US patent No.4331795, specifically described an example that is equal to mixing cured system, in a kind of composition, used the cobalt salt accelerator, and in another composition, used hydrogen peroxide.Also can prepare epoxy polymer, this can carry out cationic polymerization by fusion reactive diluent and cyclic monomer and solidify to realize UV.For example, by oligomer,, can realize the cationic curing of the UV initiation of polyurethane as by Alied Signal Inc. manufacturing according to vinethene and polycarbamate formation.
Various other embodiments also are feasible.The PIE material provides a kind of constituent that gives polymers, mainly is to cause to solidify, and ignores the potpourri that LC/ gives polymers.Be part PIE material main the composition, deposits on one or more desired spacing unit in the viewing area, therefore, can guarantee to cause and solidify and only carry out from desired position.The main composition composition of just having mentioned can be a light trigger, and it activates by splitting when being exposed to UV or visible light.By regulating the controllable intensity system photopolymerization rate of light source.Rate of diffusion in the temperature control phase separation that reacts by adjusting.In polymerization process, can change photopolymerization rate, to form multilayer, the structure of composition polymer/LC.By the degree of mixing may command of regulating LC and the giving polymers speed that is separated.By regulating LC and give the absolute and relative viscosity of polymers, the may command speed that is separated.Before apparatus for assembling, the partition unit can apply with accelerator lacquer or light trigger, and the dry method jet deposition is on one or more matrix then.Also can deposit the partition unit by the wet spraying method, wherein, as the deposition carrier solution or strictly form by accelerator or light trigger, perhaps form by both, perhaps two kinds of formation of these compounds and solvent, regulate its concentration to obtain the material of Sq, fully give polymers in the viewing area around the polymerization partition.Partition may be mixed in in the solution of accelerator or light trigger, and solution with liquid form, directly is distributed in macroscopical zone on the matrix by methods such as transfer pipet, silk screen or syringes.The macroscopic view zone can be the periphery outside, therefore, can automatically obtain the limit sealing that shows during polymerization.The partition unit can be a porous structure, accelerator or light trigger are adsorbed onto in the porous matrix, increase requiring to be positioned at the percentage by weight of zone accelerator or light trigger, and the mutual penetration that better polymkeric substance and partition unit are provided, it is bonding to offer the best thus.The partition unit can be formed by glass, usually with the form of pearl or rod, it is corroded to increase improve bonding surface area then.Before with accelerator or light trigger coated glass partition, on the glass partition that does not have corrosion or corroded, can apply the short stick of last layer or multilayer, such as, silane coupling agent, the partition unit can be mixed in light trigger or the accelerator, and it is that activity resembles desired concentration in the viewing area in district that its concentration will be higher than.Potpourri is deposited on the matrix by printing or transfer pipet method, and pixel region or the neighboring area of image do not occur in entering into, additional carrier is provided like this, and can negatively influencing have not been arranged the contrast or the quality of image.Initiating agent can be only hot activation, perhaps hot activation and photoactivation, perhaps other Activiation methods.The selection of polymkeric substance is also solidified the initial combination of matrix to limit subsequently, and is therefore that two matrix are compressed together, just as described above to increase the permanance that shows, when polymkeric substance is positioned at around the partition unit, at this moment effective especially.The partition unit can be one or more pieces extendible hole films, when being laminated between matrix, is the unit that is determining the spacing between the matrix.
In the present embodiment and other embodiments, a matrix or a plurality of matrix can be glass or other hard materials.
In another embodiment, comprise that one or more unstructuredness polymerizations cause or strengthen (PIE) unit, (this unstructuredness PIE unit is with more than a matrix not contact to its thickness less than the size of partition thing, therefore and do not provide direct extrusion structure carrier), light trigger, accelerator or other polymerization reinforcing materials are coated on unstructuredness PIE (NSPIE) unit, perhaps are included in wherein.
Other embodiments of the present invention are in following claim.
Claims (18)
1. the method for a working fluid crystal device, it comprises:
Be filled in two spaces between the matrix of facing with the potpourri that gives polymers and liquid crystal material,
Provide outside resources with initiated polymerization, wherein, when polymerization was carried out, being separated of polymkeric substance and liquid crystal generally also carried out,
After initiated polymerization and before polymerization finishes, regulate one or both parameter influence in polymerization rate and the speed that is separated, so that along the variation that produces paradigmatic structure perpendicular to two directions of facing matrix, wherein, variation is the result who regulates the polymerization rate and the speed that is separated in polymerization process.
2. according to the method for claim 1, feature is, in liquid crystal indicator, form the ground floor and the second layer at least, first and second layers can superpose each other, and be positioned at along perpendicular to two different spacing in the face of the matrix direction, wherein first and second layers structure is different, and this is because in the cambial time, due to polymerization is different with the speed that is separated.
3. according to the method for claim 1, feature is, in the time that forms structure, because polymerization is different with the speed that is separated, so the variation in the paradigmatic structure is to carry out in a continuous manner.
4. according to the method for claim 1 or 2, feature is that polymerization rate is adjustable.
5. according to the method for claim 4, feature is, by regulating the intensity of light source that influences polymerization rate, to regulate polymerization rate.
6. according to the method for claim 5, feature is that light source is a ultraviolet light.
7. according to the method for claim 1 or 2, feature is that the speed that is separated is adjustable.
8. according to the method for claim 7, feature is, regulates temperature with the adjusting speed that is separated.
9. according to the method for claim 2, feature is that ground floor mainly is a polymkeric substance.
10. according to the method for claim 9, feature is that the second layer mainly is the potpourri of polymkeric substance and liquid crystal material.
11. according to the method for claim 10, feature is also to comprise the 3rd layer, in cambial time course, because polymerization is different with the relative speed that is separated, so the structure of the ground floor and the second layer is different.
12. according to the method for claim 11, feature is that the 3rd layer mainly is liquid crystal material.
13. according to the method for claim 11, feature is that the second layer contains the droplet of liquid crystal material around polymkeric substance.
14. according to the method for claim 13, feature is that the liquid crystal droplet contacts with matrix.
15. according to the method for claim 2, feature is, giving polymers and liquid crystal is a kind of like this composition, and polymerization is to take place under such condition,, gives the degree of mixing of polymers and liquid crystal material by change that is, can determine the structure of the ground floor and the second layer.
16. according to the method for claim 2, feature is, giving polymers and liquid crystal is a kind of like this composition, and polymerization is to take place under such condition,, gives the viscosity of polymers and liquid crystal by change that is, can determine the structure of the ground floor and the second layer.
17. according to the method for claim 16, feature is that viscosity is the relative viscosity of giving polymers and liquid crystal.
18. according to the method for claim 17, feature is that viscosity is the absolute viscosity of giving polymers and liquid crystal.
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| US26823501P | 2001-02-12 | 2001-02-12 | |
| US60/268,235 | 2001-02-12 | ||
| US09/883,083 | 2001-06-15 | ||
| US09/883,083 US6618114B2 (en) | 2001-02-12 | 2001-06-15 | Electrooptical displays with multilayer structure achieved by varying rates of polymerization and/or phase separation during the course of polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1503922A true CN1503922A (en) | 2004-06-09 |
| CN1276294C CN1276294C (en) | 2006-09-20 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB028070291A Expired - Lifetime CN1276294C (en) | 2001-02-12 | 2002-02-12 | Electrooptical display with multilayer structure achieved by varying rates of polymerization and/or phase separation |
Country Status (6)
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| EP (1) | EP1360548B1 (en) |
| JP (1) | JP4034186B2 (en) |
| KR (1) | KR100831236B1 (en) |
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| AT (1) | ATE347123T1 (en) |
| DE (1) | DE60216420T2 (en) |
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| DE102006052606B4 (en) | 2006-11-08 | 2008-09-18 | Leonhard Kurz Gmbh & Co. Kg | Process for the preparation of PDLCDs |
| KR101010579B1 (en) * | 2008-12-17 | 2011-01-24 | (주)에이엔티이십일 | Multi-Disk Diffuser |
| DE102010010448A1 (en) | 2010-03-01 | 2011-09-01 | LÜTH & DÜMCHEN Automatisierungsprojekt GmbH | Materials is superimposed on outer surface of object as layer, where material is locally changed in its optical appearance on electric or electronic driveway, where device comprises mechanical, electrical and electronic components |
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| JP2831521B2 (en) * | 1992-12-17 | 1998-12-02 | シャープ株式会社 | Ferroelectric liquid crystal display device and method of manufacturing the same |
| KR100277626B1 (en) * | 1993-06-23 | 2001-01-15 | 김순택 | Manufacturing Method of Liquid Crystal Display |
| KR0171444B1 (en) * | 1993-12-27 | 1999-03-20 | 모리시다 요이치 | Polymer dispersion type liquid crystal panel, method of manufacturing the same and liquid crystal display device |
| JP3068400B2 (en) * | 1994-03-17 | 2000-07-24 | シャープ株式会社 | Manufacturing method of liquid crystal display device |
| JP2000206515A (en) * | 1998-11-13 | 2000-07-28 | Matsushita Electric Ind Co Ltd | Light controlling body, optical device, electric device and production of the same |
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2002
- 2002-02-12 JP JP2002572494A patent/JP4034186B2/en not_active Expired - Lifetime
- 2002-02-12 CN CNB028070291A patent/CN1276294C/en not_active Expired - Lifetime
- 2002-02-12 EP EP02723135A patent/EP1360548B1/en not_active Expired - Lifetime
- 2002-02-12 KR KR1020027009595A patent/KR100831236B1/en active IP Right Grant
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| JP4034186B2 (en) | 2008-01-16 |
| EP1360548B1 (en) | 2006-11-29 |
| JP2004523802A (en) | 2004-08-05 |
| CN1276294C (en) | 2006-09-20 |
| EP1360548A1 (en) | 2003-11-12 |
| ATE347123T1 (en) | 2006-12-15 |
| EP1360548A4 (en) | 2005-07-20 |
| DE60216420D1 (en) | 2007-01-11 |
| KR100831236B1 (en) | 2008-05-22 |
| DE60216420T2 (en) | 2007-10-04 |
| KR20030068391A (en) | 2003-08-21 |
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